Manufacture of



Patented Mar. 16, 1948 MANUFACTURE or 2:4-DIAMINO-1:3:5-

mznms Adolf Griin, Basel, Switzerland, assignor to J. R.

Ge xy A. G., Basel, Switzerland No Drawing. Application March 13, 1942,Serial No. 434,624. In Switzerland April 25, 1939 10 Claims. 1

This application is a continuation-impart of my U. S. patent applicationSer. No. 327,521, filed on April 2, 1940, now abandoned.

It is known that by heating fatty acid guanidine salts2:4-diamino-1r3z5-triazines, such as for example formoguanamine or thediamino-cyanurohydrogen of the formula NH YF H can be obtained fromguanidine formate or a mixture of guanidine sulfate and alkali formate.According to this reaction the homologous guanamines are alsoobtainable. As the last one the oenanthylic acid still gives aguanamine, but at the higher fatty acids however the reaction occurs inanother direction. The yield, as indicated in the literature, cannot besaid to be good. From 50 parts of guanidine salt only 5 parts ofguanamine are obtained on the average.

Subsequent work has shown that the above mentioned reaction proceeds byway of the diguanide and that accordingly the guanamines can also bemade by heating from fatty acid diguanide salts. In this case also thereaction does not take place smoothly, since secondary reactions(formation of ammeline and so on) may become the main reaction, as isknown for the formation of acetoguanamlne. The reaction of diguanidewith fatty acid esters, e. g. formic acid ethyl ester is-it istrue-applicable for the manufacture of formoguanamine, but for theformation of the higher homologues it fails as well as the abovementioned processes.

Finall it is still known to interact diguanide with benzoylchloride inthe presence of caustic soda. It has been found also in this case thatthe yields of phenylguanamine are extremely bad.

The other reactions for the formation of the guanamines may bedisregarded, since they all start from expensive, complicated compounds,such as amidines, nitriles and so forth, and are therefore notinteresting.

Now it has been found that surprisingly the 2:4-diamino-1:3:5-triazinesare obtainable very readily and in a smooth manner by the reaction ofdiguanides with carboxylic acid-halides in presence of non-causticalkalies. Thus, the higher hoinologues, which until now have not beenaccessible by interaction of fatty acids with guanidines, as well as aseries of new substitution prod- 5 nets are easily obtainable by aspecial choice of the diguanide derivatives and of the carboxylic acidchlorides.

The reaction of the cyanoguanidines, which, if desired, may besubstituted, with the carboxylic acid halides generally proceedsrelatively easily; it also begins when using relatively high molecularinitial products already at temperatures of about 100 C. and proceeds atsomewhat higher temperatures in the most cases practically completely,contrarily to the known processes, without formation of disturbinglay-products. The products themselves are constitutionally determined bythe kind of their synthesis; they are uniform.

It has been found that from the diiferent substitution products ofcyanoguanidine, such as the alkylor arylor aralkyldiguanides and so on,and from carboxylic acid halides with more than one C-atom compounds areobtained, which are doubtless 5:6-di-alkyl-2:4-diimino-tetrahydro-1:3:5-triazines, 5:6-di-aryl-2z4-diimino-tetrahydro-1:3:5-triazines and5:6-di-aralkyl-2z4-diimino-tetrahydro-l:3z5-triazines, as well ascompounds with two diflerent substituents in the positions 5 and 6, forexample alkyl and aryl or aryl and aralkyl groups and so on. They areobtained from the said initial products by the action of carboxylic acidhalides, especially the chlorides, under sufficiently energeticconditions, in presence of a hydrohalogen-bindi'ng, non-caustic agent.The reaction proceeds probably according to the following scheme:

wherein R and R mean the same or different alkyls, aryls, aralkyls,other homocyclicor heterocyclic radicals, homocyclicorheterocyclic-substituted alkyls or aryls with amino-, alkylamino-,orldialirylamino groups. alkyls and aryls with alkyioxy-, carboxylic,ether groups, also hydrocarbon radicals substituted or linked by other Ihetero-atoms than and N.

ring-closing takes place according to the following formulation: I

' B|.N.Rs Ti -NJ;

HN/ ancoo1=mo HN/ )c-rv nci' c--Nm \C-N/ is in wherein R1 and R: meanaryl, aralkyl and alkyl radicals.

The new compounds may serve as intermediate products for the manufactureof medicinal and therapeutic substances and dyestufls, but also astextile assistants, such as for example in the vatdyeing, as softeningagents and so on.

. From the technical point of view compounds of this group, whichcontain at least one higher non-aromatic hydrocarbon radical, e. g. thealkyl group of a saturated or an unsaturated fatty acid or theirmixtures, the hydrocarbon radical of a hydroaromatic acid, of resinacid, naphthenic acid, whereby this substituent may occupy the 5- aswell as the 6-position or in some cases both positions may be occupiedin such manner, are particularly interesting.

It is also important in respect of the technical use of the products,that they can be transformed into the most various derivatives for thepurpose of graduation or variation of the properties without splittingup the hetero-cycle. The aryland aralkyl derivatives can be nitrated andthe nitro derivatives reduced: they can also be suli'onated, whereby thesulfonating degree can be adjusted to the desired solubility. Thesulfuric acid radical or the SOaNa-group can also be introduced withoutthe intermediate of an aryl or aralkyl by treating a hydroxyalkylderivative with sulfuric acid or chlorosulfonic acid or by interacting achloralkyl derivative with sulflte.

Furthermore, one or more hydrogen atoms bound to nitrogen can bereplaced by alkyl, hydroxyalkyl, halogenalkyl, aminoalkyl,chlorhydroxyalkyl and so on; then the tertiary amino groups can beconverted by addition of halogenalkyl, dialkylsulfate, ethylene oxideand other alkylene oxides in presence of water into c uster naryammonium groups. When the 6-position is occupied by a methylor amethylene group it can be condensed with aldehydes, especially witharomatic aldehydes or their substitution products, thus enabling furtherreactions.

As a further possibility of variation it may be mentioned that,generally in all cases and practically in most cases, by a simpleinterchange of the substituents in 5- and G-positlon every combinationis obtainable in form of two compounds isomeric as to position. Thus itis, for example. possible to obtain by condensation of aryldiguanidewith fatty acid chloride and after-treating with dimethylsulfate andsoda the compound according to Formula A, and from alkyldiguanide witharylcarboxyl acid chloride and after-trestin: as above the isomercompound according to Formula 3:

The invention is illustrated, but not limited, by the followingexamples,the parts being by weight, except as otherwise indicated.

36 parts or phenyldiguanide are dissolved in ioo'psm of toluene, 24parts of anhydrous soda (sodium carbonate) are added and graduallycombined under stirring at SOY-60 C. with 42 parts of lauric acidchloride dissolved in the same quantity of toluene. The temperature israised gradually to 1 l0',C., and is then kept thereat for 16 hours,then the whole is allowed to cool down to 80' 0., diluted with alcohol,the solution is filtered off from the salt residue and concentrated invacuo. There is obtained without further purification the2:4-diimino-5-phenyl-8-undecyl-tetrahydro-1:3:5-triazine in form ofwhite, yellowish crystals, which are soluble in mineral and organicacids and which again precipitate on diluting. The yield amounts to 67parts instead of '12 parts'calculated, i. e. to 93% of the theory.

The use of tertiazy amines instead of soda (sodium carbonate) ords noadvantage.

If instead of a single acid chloride the mixture of the chloridesobtained from palm nut fatty acid is used, a product of a yield of about96% is obtained, which hardly can be differentiated as to constitutionand properties from that obtained from-lauric acid. Likewise theproduction with the acid chlorides of the fish-oil fatty acids or otherfatty acids from natural fats, oils, waxes and so up takes place veryeasily.

In the same manner as with phenyldiguanide the acid chloride reacts withdiguanide, methyland butyldiguanide, chlorophenyl-, oand ptoluyl,anlsidyl-, cyclohexyland py dyldiguanide. Also nitroarylandaminoaryldiguanides as well as aminoand alkylamino-alkyldlguanides suchas for example diethylaminoethyldiguanide react in suilicient degree.

Example 2 There is obtained the 2:4-diimino-5-phenyl-6rheptadecyl-tetrahydro-l :3 5-triazine in calculated yield in form ofnearly pure white crystals which after recrystallisation melt at 113-114C. This compound dissolves in organic solvents, but not in water; acidsdo not dissolve it, but disperse it in fine flakes.

The heptadecenylor naphthenyl derivatives made in the same manner fromphenyldiguanide and oleic acid or naphthenic acid (neutr. number 315)are liquid, but in their behaviour they hardly difier from thederivatives of the other acids- The other diguanides, enumerated at theend of Example 1), give similar compounds.

Example 3 100 parts of the product obtained according to Example 2 areintroduced at about 30 C. within V2 hour into 200 parts of sulfuric acidmonohydrate, then after dissolution being finished 100 parts of oleum of26 per cent strength are added and the whole is still stirred for 1 /2hours. Then the mass is stirred with a water-ice-mixture, the aqueouslayer is separated oil, the residue is pasted with water, thenneutralized with caustic soda lye and the solution concentrated byevaporation. There remain 120 parts (calculated 124 parts) of sulfonateas a greyish-white crystal meal. The sulfonate dissolves clearly inwater, the solutions are precipitated by sulfuric acid.

For the manufacture of a sulfonic acid soluble also as free acid inwater or in an excess of mineral acid stronger conditions are needed. Inthis case for example 100 parts of the substance are dissolved in amixture of 200 parts of sulfuric acid and 100 parts of oleum of 26 percent strength, the whole is stirred for 10-12 hours at about 35 C., then100 parts of oleum are further added and the whole is stirred for sixfurther hours, whereupon the sulfuric acid in excess is separated andthe neutralized reaction product isolated as above stated. The same is agrey crystal-meal which becomes nearly white by decoloring withdecoloring carbon; it readily dissolves in water and does notprecipitate n addition of sulfuric acid and so on.

Example 4 10 parts of the product obtained according to Example 2 areheated under reflux in 100 parts of toluene with 3 parts of dimethylsulfate and 5 parts of anhydrous soda (sodium carbonate) for 5 hours,and it is then filtered and the filtrate concentrated in vacuo. Theresidue is heated with the equimolecular quantity of dimethyl sulfatefor hour on the water-bath. The product forms a thick, white paste,which dissolves in water to an opalescing liquid which becomes clear, onaddition of acetic acid, becomes turbid by acids and is againprecipitated by bases.

If the intermediate product is treatedwith the double quantity ofdimethyl sulfate (i. e. molecular proportion 1:2) and soda under thesame conditions, if the methyl sulfate of sodium and the soda in excessis separated off and if dimethyl sulfate is again caused to reactWithout addition of soda, the thus obtained product is nearly completelysoluble in water to an only weakly opalescing solution even in thepresence of mineral acid. Instead of using dimethyl sulfate themethylated compound can also be made quaternary by means of ethyleneoxide or epichlorhydrine by digesting, then heating the aqueous oraqueousalcoholic solution, which may be acidified. The compound with theequimolecular quantity of stearic acid is turbidly soluble in water..

Instead of the compound used in the above example any one of the manyother compounds cited in the Examples 1 and 2 may also be employed.

Example 5 The product made according to Example 1 is dimethylated withdouble the equimolecular quantity of dimethyl sulfate and a small excessof soda, as described in Example 4 for the heptadecyl derivative. Thenthe double quantity by weightfof sulfuric acid and the same weight ofoleum of 26 per cent strength is caused to react therewith and thereaction mixture is worked up as described in Example 3. Thus there isobtained the sodium salt of the dimethyl-2:4-diimino-6-undecyl-5-phenylsulfonic acid. It forms a greyish-whitecrystal-powder, which is clearly soluble in water. Sulfuric acidprecipitates the free acid.

If the alkylation is carried out by means of diethylsulfate or anotherof the above mentioned compounds as initial material, similar productsin their appearance and behaviour are obtained.

Eaample 6 A solution of 3 parts of fencholic acid chloride in 4 parts oftoluene is caused to drop in the well stirred mixture, heated to 60 C.,of a solution of 3 parts of phenyldiguanide (or equivalent parts ofanother of the above said diguanides) in 20 parts of toluene and of 2parts of soda. The temperature increases to about C., and is then raisedto 120 C. and kept at this level for several hours. Then further 3 /2parts of soda are added and 4 parts of dimethylsulfate are caused todrop in. After heating for 5 hours under reflux the solution is filteredfrom the salt paste and the filtrate is freed in vacuo from the solvent.The residue, a yellow, soft-resinlike mass, is then dissolved at 15-20C. in the double quantity by weight of sulfuric acid, thereupon the samequantity of oleum of 25; per cent strength is gradually added, the wholeis stirred for 3 hours and the resulting sodium salt ofdimethyl-2:4-diimino 6- (1'-methyl-3'-isopropyl) cyclopentyl- 1 35-triazine-6-phenylsulfonic acid is isolated as described in Example 3for the analogous heptadecyl derivative.

Instead of the fencholic acid chloride the bromide or another acidhalide, such as for example the halide of acetic-, butyric-, valeric-,caproic. caprylic-, palmitic acid and so forth may be used. Instead ofsoda the carbonates or bicarbonates of the alkalior earth-alkali metalsor other non-caustic alkalies can be used in the above examples.

Example 7 117-118 parts of stearic acid chloride diluted with 100 partsof ehlorobenzene are allowed to drop into a solution of 79 parts of drymethyl phenyldiguanide in 500 parts of chlorobenzene, which is stirredat 70 C. with 50 parts of anhydrous sodium carbonate, whereby thetemperature rises up further to 1020 C. The whole is heated up to -120C., stirred for about 20 hours, whereupon the still hot solution isseparated from the salt paste by means of a centrifuge or by suction.Now the solution is stirred with 100 parts of anhydrous sodiumcarbonate, then 104-105 parts of dimethyl sulfate are allowed togradually run thereinto at 50 C., the whole is heated up to 1l0-120 C.for further 5 hours. while continuously stirring, centrifuged or suckedon and the chlorobenzene distilled off in vacuo. Thus, there remain 187parts, i. e. 97% of the calculated quantity of the methylated compound.

The total quantity is stirred or kneaded at 0-5 C. with 400 partsofsulfuric acid monohydrate, care being taken that the temperature doesnot rise above 1020 C. Then at a maximum of 20-25 C. 200 parts of fumingsulfuric acid (containing 26% of trioxide) are gradually added thereto.The whole is stirred for several hours until a test, afterneutralisation. is clearly soluble in water, and the mass is introducedinto 1500 parts of ice, whereupon, if neces- 7 sary, water is added,until a complete separation of the'layers has been reached, and finallythe diluted sulfuric acid is separated from the sulfonic acid remainingin an undissolved condition.

The sulfonic acid layer is stirred with water (according to the desiredpercentage of the final product with the equal or manifold quantity byweight), then 50 parts of anhydrous sodium carbonate are added theretothus separating for the greatest part the sulfuric acid aflixed to theamino groups and the whole is completely neutralised by means ofconcentrated caustic soda lye.

The compound constitutes a yellowish crystal meal which with a littlewater swells jelly-like, but is clearly soluble in some more water. Thesolution is stable towards bases and salts (the water-hardening agents).It shows excellent capillary-active properties and is suitable forvarious technical purposes, especially useful as textile assistants suchas for example as stripping and levelling agent in vat-dyeing.

The methylphenyldiguanide serving as starting material may be preparedas follows:

107 parts of monomethylaniline aredissolved in a mixture of 100 parts ofconcentrated hydrochloric acid and 400 parts of water. Then 92 parts ofdicyanodiamide are added thereto, the whole is heated for 2 hours, whilestirring, up to 105 C. and stirring continued at this temperature forfurther 18 hours. After cooling down, 140 parts of caustic soda lye of30% strength, previously diluted with 250 parts of water, are allowed togradually fiow therein and the solution, which has been warmed up toabout 35 C. is stirred for half an hour, whereupon the reaction productis precipitated out by the addition of 150 parts of sodium chloride.After exhausting by suction and drying of the precipitate there areobtained about 1'70 parts of N-methyl- N-phenyldiguanide, that is to saya yield of about 90% of the theory.

Instead of pure methyl aniline there can also be used a raw mixture ofmonoand dimethylaniline resulting from the methylation of aniline. Thusfor example instead of 107 parts of methylaniline 267 parts of a mixtureof 60% of dimethyland 40% of monomethylaniline are worked up, as aboveindicated, in a hydrochloric solution with dicyanodiamide and thereaction mixture is then maintained at a temperature of 70-80 C. untilthe separation in two layers has taken place. The upper layer which isnow separated consists of 155-160 parts of dimethylaniline which thus isisolated in a yield of 97-98% of the theory. The lower aqueous layercontains the methylphenyldiguanide hydrochloride which is separated outin the same manner and with the same yield as above indicated, by meansof caustic soda lye and sodium chloride.

Example 8 41 parts of N-ethyl-N-phenyldiguanide or the correspondingquantity of the dry precipitate containing sodium chloride, as obtainedaccording to the indications given below, diluted with manifold theweight of chlorobenzene are caused to react in the presence of 24 partsof anhydrous sodium carbonate first at 70-80 C., finally at 110-120 C.with 56 parts of stearic acid chloride; then it is filtered from thesaltpaste and, after the addition of 45 parts of anhydrous sodium carbonate,the filtrate is treated with 50 parts of dimethyl sulfate whereby thetemperature of initially 50 C. is finally increased to 110 C. Afterdistillation of the chlorobenzene in 8 vacuo, there remain 88 parts(calculated 92 parts) of dimethyl derivative.

For the sulfonation this derivative is dissolved in the double quantityby weight of sulfuric acid of strength and treated with oleum containing28% of 803, until a sample has become soluble in caustic alkali. Theusual working up yields more than 100 parts of sulfonate which,

.with regard to appearance and solubility, hardly differs from theproduct obtained according to Example 7.

The starting material can be prepared as follows:

240 parts of monoethylaniline dissolved in a mixture of 200 parts ofconcentrated hydrochloric acid and 700 parts of water are stirred for 20hours at C. with 184 parts of dicyanodiamide. After cooling, 320 partsof caustic soda lye of 30% strength diluted with 500 parts of water areadded thereto. By precipitating by means of 500 parts of sodiumchloride, centrifuging and drying there are obtained about 350 parts ofN-ethyl-N-phenyldiguanide.

In the same manner as monoethyland monomethylaniline the N-ethylandN-methyltoluidines, the N-alkylxylidines, -anisidines, -phenetidines andother alkylarylamines substituted in the aromatic nucleus can also becondensed with dicyanodiamide and the diguanide derivatives thusobtained be caused to react first with acid chloride, then withdialkylsulfate and finally be sulfonated.

The conversion of the alkyl-aralkyl-diguanides with acid chlorides andthe further production of derivatives are carried out in the samemanner. However, in these cases the preparation of the starting productsby the reaction of the amine hydrochloride with dicyano diamide is oftennot possible or not productive. The starting products may then beproduced analogously to the preparation of dialkyl-diguanides by way ofthe copper complex salts. For example, dicyanodiemide gives, in anaqueous alcoholic medium in the presence of the equimolecular quantityof copper sulfate, with an excess of ethyl- (or methyl-) benzylamine(obtained by a condensing hydrogenation of benzaldehyde with ethylamine,B. R12 mm. -112 C.) the complex salt from which the copper is eliminatedin a known manner by means of hydrogen sulfide, while the N- ethyl- (orN-methyl-)N-benzyldiguanide is isolated.

Example 9 57 parts of the methylphenyldiguanide obtained according toExample 7 are condensed in the presence of 45 parts of anhydrous sodiumcarbonate with 60 parts of the chlorides of the palm nut fatty acid. Theintermediate product is treated first with 76 parts of dimethyl sulfate(1. e. two molecules per one molecule of the substrate) in the presenceof 90 parts of anhydrous sodium carbonate, then, after the separation ofthe resulting sodium methylsulfate and of excess sodium carbonate, witha further quantity of '16 parts of dimethylsulfate. without addition ofsodium carbonate. After having expelled the diluent such as e. g.chlorobenzene in vacuo the final product is obtained in form of asemi-solid gel. It is completely clearly soluble in water and the highlycapillary-active solution is stable towards acids, while by the additionof bases there is caused a turbidity or precipitation respectively.

When in the second (last but one) reaction phase, the alkylation in thepresence of sodium carbonate, the dimethyl sulfate is replaced by theequivalent quantity, that is to say by 92 parts of diethyl sulfate, oneobtains by the subsequent treatment with dimethyl sulfate alone anequivalent final product which is clearly soluble in water. If, however,in the last reaction phase the dimethyl sulfate is replaced by diethylsulfate, the final product gives with water an opalescing solution andthis independently of whether in the last but one phase there has beenused dimethyl sulfate or diethyl sulfate.

If in the first reaction phase there is used technical stearic acidchloride'and if the resulting intermediate product is worked up, asabove indicated, with dimethyl or diethyl sulfate first in the presenceand then in the absence of sodium carbonate, the final product is,except for the somewhat greater consistency, equivalent to the productprepared by means of palm nut fatty acid chloride. cocos acids, it is,however, more difficult to obtain products which are clearly soluble inwater.

Example 70 parts of the ethylphenyldiguanide prepared according toExample 8 are dissolved in chlorobenzene, then 45 parts of anhydroussodium carbonate are added thereto and about 65 parts of palm nut fattyacid chloride are allowed to flow thereinto at 70 C., whereupon thereaction is completed by gradually increasing the temperature up to110-l20 C. and the intermediate product is isolated.

By the reaction of first 76 parts of dimethyl sulfate in the presence of90 parts of anhydrous sodium carbonate and of a further equal quantityof dimethyl sulfate without addition of sodium carbonate a product isobtained which with regard to its nature and behaviour, especially withrespect to complete water-solubility, resembles the product obtainedaccording to Example 9.

Also in this case the dimethyl sulfate may be replaced in the last butone reaction phase by the corresponding quantity of diethyl sulfatewithout impairing the solubility of the final product, while the use ofdiethyl sulfate in the last phase gives products whose aqueous solutionsare turbid.

Example 11 152 parts of methylphenyldiguanide are caused to react with180 parts of naphthenic acid chloride in the presence of 120 parts ofanhydrous sodium carbonate. The intermediate product is treated with 190parts of dimethyl sulfate or with the corresponding quantity of diethylsulfate in the presence of 200 parts of anhydrous sodium carbonate, then190 parts of dimethyl sulfate are caused to react alone with thismixture. whereby throughout all of the phases the conditions mentionedin the Examples 7 and 8 are observed. The final product constitutes aclear gel which with water gives weakly opalescing solutions.

Example 12 Methylphenyldiguanide is condensed with the equimolecuiarquantity of fencholic acid chloride and twice two-fold the equimolecularquantity of dimethyl sulfate, first in the presence and then in theabsence of sodium carbonate, is caused to react with the intermediateproduct. Thus there When using the chlorides of the is obtained aproduct giving with water strongly opalescing solutions.

I Example 13 parts of methylphenyldiguanide are conbonate. Theintermediate product is dissolved in alcohol of 90% strength, treatedwith 92 parts of epichlorhydrine and heated in the autoclave for severalhours up to -130 C., whereupon the alcohol is expelled. The residue(about 220 parts) solidifies after some time in a crystalline form. Itshows no more reaction for chlorine ions. By the interaction of 63 partsof dimethyl sulfate the said residue is converted into a moderatelyviscous liquid which gives with water weakly opalescing solutions.

What I claim is:

i. A process for the manufacture of derivatives of2z4-diamino-lz3zfi-trlazines, comprising causing a di uanide selectedfrom the group consist-' in: of diguanide, a monoalkyl substituteddiguanide, a monoaryl substituted diguanide of the benzene series, analkylaryldiguanide of the benzene series and an alkylbenzyldiguanide toreact with a carboxylic acid halide in presence of ahydrohalogen-binding agent selected from the group consisting of thealkali metal carbonates, alkaline earth metal carbonates, alkali metalblcarbonates and alkaline earth metal bicarbonates.

2. A process as claimed in claim 1, wherein the reaction components areso chosen that the final product contains at least one organicsubstituent with more than 6 C-atoms in the 5-position.

3. A process as claimed in claim 1, wherein the reaction components areso chosen that the final Product contains at least one organicsubstituent with more than 6 C-atoms in the 6-position.

4. A process for the manufacture of a 2:4-diamino-1:3:5-triazinederivative, comprising reacting a diguanide selected from the groupconsisting of diguanide, a monoalkyl substituted diguanide, a monoarylsubstituted diguanide of the benzene series, an alkylaryldiguanide ofthe benzene series and an alkylbenzyldiguanide to react with stearicacid chloride in presence of an alkali metal carbonate.

5. A process for the manufacture of a 2:4-diamino-1:3:5-triazinederivative, comprising reacting a monoaryldiguanide of the benzeneseries witha carboxylic acid halide containing at least 6 carbon atomsin presence of an alkali metal carbonate.

6. A process for the manufacture of a 2:4-diamino-1:3:5-triazinederivative, comprising reacting phenyldiguanide with stearic acidchloride in presence of an alkali metal carbonate.

7. A process for the manufacture of a 2:4-diamino-1:3:5-triazinederivative, comprising reacting phenylmethyldiguanide with stearlc acidchloride in the presence of an alkali metal carbonate.

8. As new compound 2:4-diimino-5-phenyl-6-heptadecyl-tetrahydro-l13:5-triazine, being white crystals, melting at113-114 C., soluble in organic solvents, insoluble in water.

9. The sodium salt of a sulphonic acid of 2:4-diimino-5-phenyl -6-heptadecyl-tetrahydro-l :3:5- triazine, being a substantially whitecrystal meal, soluble in water.

10. The 2:4-diamino-1z3z5-triazine derivatives of the following generalformula 11 wherein A means an aliphatic radical with more Number NameDate than 6 carbon atoms and B means an aromatic 2, 02,828 Bruson June4, 1940 radical or the benzene series. 2.2 0.478 Schmidt Jan. 20, 1942wow GRU'N. 1,549,901 Bonhote Aug.18, 1925 FORE! N TENT REFERENCES CITED'G PA S Number Country Date The iollowin: references are of record in the4 5, 5 Great Britain 1937 me this 10 OTHER REFERENCES [mum IENI Annalen378, pp. 167, 180, 181. Number Name Date Berlchte do Deut. Gees. 24, pp.2594-2601.

2,217,030 Simona O t- 1 J. Prakt. Chem.2 (84), p. 403. 2,258,130 BruaonOct. '1, 1941

